Patent GB-432486-A (GB)
Title: Improvements in or relating to dry adhesives
IPC: C09J103/02
Filed: 1934-01-15
Abstract: Adhesive compositions in a dry powdered form comprise known organic adhesives with the addition of lime-stable wetting agents corresponding to the formula RmXn where R denotes a substituted or unsubstituted higher aliphatic or hydroaromatic residue containing at least eight carbon atoms, e.g. the residues of higher fatty alcohols or fatty acids or the residues of napthenic or resinic acids or the corresponding alcohols; X denotes a water-solubilizing group combined with R in the a , b  or g  position in the case of aliphatic compounds and in the case of hydroaromatic compounds directly attached in the nucleus or in the a , b  or g  position from the free end of a side chain, and m, n are at least one.  Suitable water-solubilizing groups are the sulphonic acid group; the carboxyl group; the sulphuric acid ester group; the N-sulphonic acid group; the phosphoric acid ester group; the thiosulphuric acid ester group; the quaternary ammonium group; or salts thereof; the additive compounds of amines with acids; and groups in which polyoxy or polyether groups are accumulated, and these groups may be linked to the higher aliphatic or hydroaromatic residue either directly or through an oxygen, sulphur or nitrogen atom.  Suitable organic adhesives include animal glues and gelatines, natural or synthetic resins, adhesives having a base of animal or vegetable albumins or proteins, casein, soluble starch and disintegration products thereof, such as dextrin.  Suitable wetting agents are the salts of sulphuric acid, phosphonic acid and thiosulphonic acid esters of higher fatty alcohols; a -sulphonic acids of paraffins or fatty acids; hydroxy-alkyl sulphonic acids, e.g. b -hydroxy ethane sulphonic acid and its homologues which have been etherified by higher alkyl residues or esterified by higher fatty acid residues; sulphuric acid, phosphoric acid and thiosulphuric acid esters of mono- or poly-glycols and glycerols which are partially etherified by higher alkyl residues or esterified by higher fatty acid residues or by resinic or naphthenic acids; higher alkyl esters of sulphocarboxylic acids such as sulphoacetic acid and its homologues; sulphuric acid, phosphoric acid and thiosulphuric acid esters of sulphones having a higher alkyl residue and a lower aliphatic residue containing at least one hydroxyl group; sulphuric acid, phosphoric acid and thiosulphuric acid esters of lower aliphatic hydroxy-carboxylic acids esterified by higher aliphatic or hydroaromatic residues.  The ester-like bond between the higher aliphatic or hydroaromatic residue and the alkyl residue containing the water-solubilizing group may also be replaced by the carbonamide or sulphonamide bond.  Other suitable compounds are the carbonic acid esters and urethanes, substituted by a higher aliphatic or hydroaromatic residue and a residue containing a water-solubilizing group; lime-stable carboxylic acids containing a higher aliphatic or hydroaromatic residue, e.g. salts of acetic acid substituted by higher alkyloxy or alkyl-mercapto residues as the sodium salt of thiodiglycollic acid-mono-n-octyl ester; compounds containing numerous poly-oxy or poly-ether groups in addition to a higher aliphatic or hydroaromatic residue such as may be obtained by condensing alkylene oxides with higher alcohols and carboxylic acids, for example as described in Specification 409,030; sugars and sugar alcohols which have been partially etherified by higher alkyl residues or esterified by higher fatty acid residues, and the products of the reaction of alkylene oxides on sugars and sugar alcohols.  The wetting agents may be added in the form of powder to the powdered adhesives, or the solutions may be mixed and subsequently dried; they are preferably added in quantities between 0,1 and 1 per cent of the adhesives.  According to examples, (1) 100 kgm. of cold water-soluble starch are mixed with 2 kgm. of the sodium salt of the sulphuric acid esters of a mixture of octyl, decyl, dodecyl, tetradecyl and cetyl alcohols; (2) 100 kgm. of cold water-soluble starch are mixed with 1,3 kgm. of the sodium salt of the thiosulphuric acid esters of a mixture of glycollic acid octyl, decyl, dodecyl and tetradecyl esters.  Samples have been furnished under Sect. 2 (5) comprising (A) 100 kgm. of cold water-soluble starch mixed with 2 kgm. of a mixture of the sodium salts of sulphonated higher fatty alcohols; (B) 100 kgm. of cold water-soluble starch mixed with 1,3 kgm. of a mixture of compounds of formula R.O.CO.CH2S.SO3Na where R is C8H17, C10H12 and C12H25; (C) 100 kgm. of cold water-soluble starch mixed with 1 kgm. of sodium salt of dodecone-a -sulphonic acid; (D) 100 kgm. of cold water-soluble starch mixed with 2 kgm. of the disodium salt of the phosphoric acid ester of oleyl alcohol; (E) 100 kgm. of cold water-soluble starch mixed with 0,5 kgm. of sodium salt of the sulphonation product of perhydric menapthyl cresol, where menapthyl denotes the naphthyl-methyl residue; (F) 100 kgm. of cold water-soluble starch mixed with 1 kgm. of sodium salt of N-oleic-N-methylamino-ethane-sulphonic acid; (G) 100 kgm. of cold water-soluble starch mixed with 0,2 kgm. of sodium salt of the sulphonation product of a mixture of higher mono-alkylglycerol ethers, where alkyl is C12H25, C14H29, C16H33, and C18H37; (H) 100 kgm. of cold water-soluble starch mixed with 1 kgm. of a mixture of compounds of formula <FORM:0432486/IV/1> where R is C12H25, C14H29, C16H33 and C18H37; (I) 100 kgm. of cold water soluble starch mixed with 1 kgm. of the reaction product of 20 mols. of glycide with 1 mol. of a mixture of higher fatty alcohols; (K) 100 kgm. of dextrin mixed with 2 kgm. of sodium salt of dodecylmercapto acetic acid; (L) 100 kgm. of casein mixed with 0,2 kgm. of sodium salt of the sulphonation product of perhydric menaphthyl cresol; (M) 100 kgm. of animal glue mixed with 1 kgm. of the above salt. Specification 409,030 is referred to.  Reference has been directed by the Comptroller to Specification 392,342 (as open to inspection under Sect. 91 of the Acts).ALSO:Adhesive compositions in a dry powdered form comprise known organic adhesives with the addition of lime-stable wetting agents corresponding to the formula Rm Xn where R denotes a substituted or unsubstituted higher aliphatic or hydroaromatic residue containing at least eight carbon atoms e.g. the residues of higher fatty alcohols or fatty acids or the residues of naphthenic or resinic acids or the corresponding alcohols; X denotes a water-solubilizing group combined with R in the a , b  or g position in the case of aliphatic compounds and in the case of hydroaromatic compounds directly attached in the nucleus or in the a , b  or g  position from the free end of a side chain, and m, n are at least one.  Suitable water-solubilizing groups are the sulphonic acid group: the carboxyl group: the sulphuric acid ester group; the N-sulphonic acid group: the phosphoric acid ester group: the thiosulphuric acid ester group: the quaternary ammonium group; or salts thereof: the additive compounds of amines with acids; and groups in which polyoxy or polyether groups are accumulated, and these groups may be linked to the higher aliphatic or hydroaromatic residue either directly or through an oxygen, sulphur or nitrogen atom.  Suitable organic adhesives include animal glues and gelatines, natural or synthetic resins, adhesives having a base of animal or vegetable albumins or proteins, casein, soluble starch and disintegration products thereof, such as dextrin.  Suitable wetting agents are the salts of sulphuric acid, phosphoric acid and thiosulphuric acid esters of higher fatty alcohols; a -sulphuric acids of paraffins or fatty acids; hydroxy-alkyl sulphonic acids e.g. b -hydroxyethane sulphonic acid and its homologues, which have been etherified by higher alkyl residues or esterified by higher fatty acid residues; sulphonic acid, phosphoric acid and thiosulphuric acid esters of mono- or poly-glycols and mono- or polyglycerols which are partially etherified by higher alkyl residues or esterified by higher fatty acids or by resinic or napthenic acids; higher alkyl esters of sulphocarboxylic acids such as sulphoacetic acid and its homologues; sulphuric acid, phosphoric acid and thiosulphuric acid esters of sulphones having a higher alkyl residue and a lower aliphatic residue containing at least one hydroxyl group; sulphuric acid, phosphoric acid and thiosulphuric acid esters of lower aliphatic hydroxy-carboxylic acids esterified by higher aliphatic or hydroaromatic residues.  The ester-like bond between the higher aliphatic or hydroaromatic residue and the alkyl residue containing the water-solubilizing group may also be replaced by the carbonamide or sulphonamide bond.  Other suitable compounds are the carbonic acid esters and urethanes, substituted by a higher aliphatic or hydroaromatic residue, and a residue containing a water-solubilizing group; lime-stable carboxylic acids containing a higher aliphatic or hydroaromatic residue e.g. salts of acetic acids substituted by higher alkyloxy or alkylmercapto residues as the sodium salt of thiodiglycollic acid-mono-n-octyl ester; compounds containing numerous poly-oxy or poly-ether groups in addition to a higher aliphatic or hydroaromatic residue such as may be obtained by condensing alkylene oxides with higher alcohols and carboxylic acids, for example as described in Specification 409,030, [Group IV]; sugars and sugar alcohols which have partially etherified by higher alkyl residues or esterified by higher fatty acid residues and the products of the reaction of alkylene oxides on sugar and sugar alcohols.  The addition of the above wetting agents is stated to prevent the tendency to cake on storage, to promote the spreading power of the adhesives and to render the operation of swelling or solution more uniform.  The wetting agents may be added in the form of powder to